CA1255436A - Sulphur-containing polymers - Google Patents
Sulphur-containing polymersInfo
- Publication number
- CA1255436A CA1255436A CA000502113A CA502113A CA1255436A CA 1255436 A CA1255436 A CA 1255436A CA 000502113 A CA000502113 A CA 000502113A CA 502113 A CA502113 A CA 502113A CA 1255436 A CA1255436 A CA 1255436A
- Authority
- CA
- Canada
- Prior art keywords
- weight
- parts
- styrene
- mixture
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/06—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Sulphur-containing polymers of styrene, .alpha.-methyl styrene, p-methyl styrene, vinyl toluene, acrylonitrile or methyl methacrylate or mixtures thereof with a limiting viscosity of from 2 to 15 ml/g (measured in dimethyl formamide at 25°C) and a sulphur content of from 1.15 to 3.95% by weight, whereby at least 90% by weight of the incorporated sulphur is present as a constituent of terminal C1-18-thioalkyl groups. The polymers improve the flowability of acrylonitrile butadiene styrene (ABS) polymers.
Sulphur-containing polymers of styrene, .alpha.-methyl styrene, p-methyl styrene, vinyl toluene, acrylonitrile or methyl methacrylate or mixtures thereof with a limiting viscosity of from 2 to 15 ml/g (measured in dimethyl formamide at 25°C) and a sulphur content of from 1.15 to 3.95% by weight, whereby at least 90% by weight of the incorporated sulphur is present as a constituent of terminal C1-18-thioalkyl groups. The polymers improve the flowability of acrylonitrile butadiene styrene (ABS) polymers.
Description
231~-618~
The present invention provides sulphur-containing poly-mers with terminal thioaLkyl groups which have a limiting viscos-ity of from 2 to 15 ml/g (measured in DM~ at 25C) and a sulphur content of from 1.15 to 3.95~ by weight.
Acrylonitrile butadiene styrene (ABS) polyMers have a good property combination of high impact strength, good chemical-resistance and easy processibility. In spite of this, in special cases, such as with ABS mixtures with a high rubber content, a flowability of the thermoplastic material can result which is insufficient in practice for demands of modern processing tech-nology. Remedy through addition of low molecular weight flow auxiliaries such as ethylene diamine bisstearoyl amide or calcium stearate often results in strength losses, reduced dimensional stability under heat or migration of the added lubricant.
An improvement in the flowability by increasing -the processing temperature can usually only be obtained at the cost of a partial thermooxidative degradation in the rubber phase.
The need thus existed for a thermoplastic material which can be used to improve the flowability of ABS thermoplast resins, ~0 which has no negative influences on the ABS properties, parti-cularly strength and dimensional stability under heat, and which opposes a thermooxidative decomposition of the rubber phase.
According to one aspect of the present invention there is provided sulphur-containing polymers of styrene, -methyl styrene, p-methyl styrene, vinyl toluene acrylonitrile or methyl methacrylate or mixtures thereof with a limiting viscosity of from
The present invention provides sulphur-containing poly-mers with terminal thioaLkyl groups which have a limiting viscos-ity of from 2 to 15 ml/g (measured in DM~ at 25C) and a sulphur content of from 1.15 to 3.95~ by weight.
Acrylonitrile butadiene styrene (ABS) polyMers have a good property combination of high impact strength, good chemical-resistance and easy processibility. In spite of this, in special cases, such as with ABS mixtures with a high rubber content, a flowability of the thermoplastic material can result which is insufficient in practice for demands of modern processing tech-nology. Remedy through addition of low molecular weight flow auxiliaries such as ethylene diamine bisstearoyl amide or calcium stearate often results in strength losses, reduced dimensional stability under heat or migration of the added lubricant.
An improvement in the flowability by increasing -the processing temperature can usually only be obtained at the cost of a partial thermooxidative degradation in the rubber phase.
The need thus existed for a thermoplastic material which can be used to improve the flowability of ABS thermoplast resins, ~0 which has no negative influences on the ABS properties, parti-cularly strength and dimensional stability under heat, and which opposes a thermooxidative decomposition of the rubber phase.
According to one aspect of the present invention there is provided sulphur-containing polymers of styrene, -methyl styrene, p-methyl styrene, vinyl toluene acrylonitrile or methyl methacrylate or mixtures thereof with a limiting viscosity of from
2 to 15 ml/g, pre-Eerably Erom 3 to 12 ml/g (measured in DMF at Le A 23 559-CA ~$
~ -- 1 --.
, :, ; :
5~
25 C) and a sulphur content of from 1.15 to 3.95% by weight, preferably from 1.25 to 2.40% by weight, whereby at least 90% by weight of the incorporated sulphur is present as a constituent of terminal Cl 18-thioalkyl yroups.
According to another aspect of the present invention there is provided the use of the sulphur-containing polymers as defined above as a combined agent for improving the flowability and for protection for ABS polymers against thermooxidative damage.
According to a further aspect of the present invention there is provided a process for the production of sulphur-contain-ing polymers of styrene, ~-methyl styrene, p-methyl styrene, vinyl toluene, acrylonitrile or methyl methacrylate or mixtures thereof with a limiting viscosity of from 2 to 15 ml/g (measured in dimethyl formamide at 25C), characterised in that the monomer or the monomer mixture is polymerised in the presence of a Cl 18-alkyl mercaptan or mixtures thereof in quantities of from 4 (0.503 . X + 1.222) % by weight to (1.728 . X ~ 4.197) % by weight (based on the sum of the monomer and mercaptan quantity), whereby X represents the number of carbon atoms in the alkyl mer-captan.
According to a still further aspect of the present inven-tion there is provided thermoplastic mixtures containing graft polymers A), copolymers B) and polymers C), characterised in that they contain a sulphur-containing polymer C) of styrene, ~-methyl styrene, p~methyl styrene, vinyl toluene acrylonitrile or methyl methacrylate or mixtures thereof with a sulphur content, intro-'.`,;
:
,:
"
,. . : .
.
,' ` ," ~ ' duced via terminal Cl 18-thioalkyl yroups, of from 1.15 to 3.95~
by weight and a limiting viscosity of from 2 to 15 ml/y (measured in dimethyl formamide at 25C) in quantities of from 0.5 to 15 parts by weight, based in each case on 100 parts by weiyht of a mixture of graft polymers A), copo:Lymers s) and polymers C).
According to another aspect of the present invention there is provided thermoplastic mixtures as defined aboYe, characterised in that they contain A) from 5 to 80 parts by weight of a graft polymer consist-lQ ing of A)l) from 5 to 90 parts by weight of a mixture of A)l)l) from 50 to 90% by weight of styrene, ~-methyl ~ hqloqe~D
styrene,~ Lea~ b~e~ styrene, methyl methacrylate or mix-tures thereof and A)1)2) from 50 to 10% by weight of (meth)acrylonitrile, methyl methacrylate, N-substituted maleimide or mixtures thereof, on A)2) from 95 to 10 parts by weight of a rubber with a glass temperature < 10C, and B) from 5 to 95 parts by weight of a thermoplastic copolymer with a Mw of from 15 000 to 200 000 (measured by light scatter or sedimentation) consisting of B)l) from 50 to 95~ by weight of styrene, ~--methyl s-tyrene, h~
-na~4~uh~ e~-styrene, methyl methacrylate or mixtures thereof, and B)2) from 50 to 5~ by weight of (meth)acrylonitrile, methyl methacrylate, maleic acid anhydride, N-substituted maleimide or . .
" , ' ', , ~Z~5~3~
mixtures thereof, whereby the sum of the parts by weiyht of graft polymer A), copolymer s) and polymer C) is in each case again 100.
Some preferred polymers accordlng to -the invention are produced by polymerizing the followiny mixtures:
Mixture 1 a) from 50 to 80 parts by weight, preferably from 55 to 75 parts by weight of (~-methyl)styrene and/or p-methyl styrene or vinyl toluene, b) from 10 to 30 parts by weight, preferably from 15 to 27.5 parts by weight of (meth)acrylonitrile and c) as many parts by weight of a Cl 18-alkyl mercaptan or mixtures thereof as produce a sulphur content of from 1.15 to
~ -- 1 --.
, :, ; :
5~
25 C) and a sulphur content of from 1.15 to 3.95% by weight, preferably from 1.25 to 2.40% by weight, whereby at least 90% by weight of the incorporated sulphur is present as a constituent of terminal Cl 18-thioalkyl yroups.
According to another aspect of the present invention there is provided the use of the sulphur-containing polymers as defined above as a combined agent for improving the flowability and for protection for ABS polymers against thermooxidative damage.
According to a further aspect of the present invention there is provided a process for the production of sulphur-contain-ing polymers of styrene, ~-methyl styrene, p-methyl styrene, vinyl toluene, acrylonitrile or methyl methacrylate or mixtures thereof with a limiting viscosity of from 2 to 15 ml/g (measured in dimethyl formamide at 25C), characterised in that the monomer or the monomer mixture is polymerised in the presence of a Cl 18-alkyl mercaptan or mixtures thereof in quantities of from 4 (0.503 . X + 1.222) % by weight to (1.728 . X ~ 4.197) % by weight (based on the sum of the monomer and mercaptan quantity), whereby X represents the number of carbon atoms in the alkyl mer-captan.
According to a still further aspect of the present inven-tion there is provided thermoplastic mixtures containing graft polymers A), copolymers B) and polymers C), characterised in that they contain a sulphur-containing polymer C) of styrene, ~-methyl styrene, p~methyl styrene, vinyl toluene acrylonitrile or methyl methacrylate or mixtures thereof with a sulphur content, intro-'.`,;
:
,:
"
,. . : .
.
,' ` ," ~ ' duced via terminal Cl 18-thioalkyl yroups, of from 1.15 to 3.95~
by weight and a limiting viscosity of from 2 to 15 ml/y (measured in dimethyl formamide at 25C) in quantities of from 0.5 to 15 parts by weight, based in each case on 100 parts by weiyht of a mixture of graft polymers A), copo:Lymers s) and polymers C).
According to another aspect of the present invention there is provided thermoplastic mixtures as defined aboYe, characterised in that they contain A) from 5 to 80 parts by weight of a graft polymer consist-lQ ing of A)l) from 5 to 90 parts by weight of a mixture of A)l)l) from 50 to 90% by weight of styrene, ~-methyl ~ hqloqe~D
styrene,~ Lea~ b~e~ styrene, methyl methacrylate or mix-tures thereof and A)1)2) from 50 to 10% by weight of (meth)acrylonitrile, methyl methacrylate, N-substituted maleimide or mixtures thereof, on A)2) from 95 to 10 parts by weight of a rubber with a glass temperature < 10C, and B) from 5 to 95 parts by weight of a thermoplastic copolymer with a Mw of from 15 000 to 200 000 (measured by light scatter or sedimentation) consisting of B)l) from 50 to 95~ by weight of styrene, ~--methyl s-tyrene, h~
-na~4~uh~ e~-styrene, methyl methacrylate or mixtures thereof, and B)2) from 50 to 5~ by weight of (meth)acrylonitrile, methyl methacrylate, maleic acid anhydride, N-substituted maleimide or . .
" , ' ', , ~Z~5~3~
mixtures thereof, whereby the sum of the parts by weiyht of graft polymer A), copolymer s) and polymer C) is in each case again 100.
Some preferred polymers accordlng to -the invention are produced by polymerizing the followiny mixtures:
Mixture 1 a) from 50 to 80 parts by weight, preferably from 55 to 75 parts by weight of (~-methyl)styrene and/or p-methyl styrene or vinyl toluene, b) from 10 to 30 parts by weight, preferably from 15 to 27.5 parts by weight of (meth)acrylonitrile and c) as many parts by weight of a Cl 18-alkyl mercaptan or mixtures thereof as produce a sulphur content of from 1.15 to
3.95~ by weight in the polymer; or d) from 7.5 to 25 parts by weight, preferably from 8 to 15 parts by weight of tert.-dodecyl mercaptan and/or n-dodecyl mer-captan or mixtures thereof;
Mixtur 2 a) from 25 to 75 parts by weight, preferably from 30 to 70 parts by weight of (~-methyl)styrene and/or p-methyl styrene or vinyl toluene, b) from 25 to 75 parts by weight, preferably from 30 to 70 parts by weight of methyl methacrylate and c) as many parts by weight of a Cl_l8-alkyl mercaptan or mixtures thereof as produce a sulphur content of from 1.15 to 3.95~ by weight in the polymer; or d) from 7.5 to 25 parts by weight, preferably from 8 to 15 parts by weight of tert.-dodecyl mercaptan and/or n-dodecyl mer-captan or mixtures thereof;
. ' ' ~' '~ "''".
: - , .
, ~5~
Mixture 3 a) from lO to 60 parts by weigh-t, preferably .Erom 20 to 50 parts by weight of (~-methyl)styrene and/or p-rne-thyl styrene or vinyl toluene, b) from 10 to 60 parts by weigh-t, preferably from 20 to 50 parts by weight of methyl methacrylate, c) from 10 to 30 parts by weight, preferably from~ to 27.5 parts by weight of (meth)acrylonitrile and d) as many parts by weight of a Cl 18-alkyl mercaptan or mixtures thereof as produce a sulphur content of from 1.15 to 3.95% by weight in the polymer; or e) from 7.5 to 25 parts by weight, preferably from 8 to 15 parts by weight of tert.-dodecyl mercaptan. and/or n-dodecyl mer-captan or mixtures thereof;
Mixture 4 a) from 50 to 80 parts by weight, preferably from 55 to 75 parts by weight of methyl methacrylate, b) from lO to 30 parts by weight, preferably from 15 to 27.5 parts by weight of (meth)acrylonitrile and c) as many parts by weight of a Cl_lg-alkyl mercaptan or mixtures thereof as produce a sulphur content of from 1.15 to 3.95% by weight in the polymer; or d) from 7.5 to 25 parts by weight, preferably from 8 to 15 parts by weight of tert.-dodecyl mercaptan and/or n-dodecyl mer-captan or mixtures thereof.
' -Preferred sulphur-containing polymers are those which have a good compatibility with ABS polymers, particularly copolymers or terpolymer~ of (nuclear o~ side-chain substituted) styrene.
The production of the polymers according to the invention can take place in a known manner by solution-~
suspension-or emulsion polymerisation or by a combination of these processes, the polymerisation in emulsion is preferred.
This is preferably carried out using anionic emulsifiers such as sodium, potassium or ammonium salts of long-chain fatty acids having from 10 to 20 carbon atoms, for example potassium oleate, alkyl sulphates having from 10 to 20 carbon atoms, alkyl aryl sulphonates having from 10 to 20 carbon atoms or alkali or ammonium salts of diproportion-ated abietic acid.
The polymerisation reaction can be carried out in a wide temperature range, it preferably ta~es place between 30C
and 100C, particularly preferably between 50C and 80C.
Suitable radical-forming initiators are organic and inorganic peroxides, inorganic persulphates such as potassium persulphate, azoinitiators such as azobisisobutyronitrile, as well as redox systems which consist of an oxidizing agent, preferably a peroxide, and a reducing agent.. Potassium persulphate is used as preferred initiator, the quantities for use are between 0.1 and 0.5% by weight (based on the monomer quantity).
The introduction of the terminal thioalkyl groups takes place by polymerisation of a mixture of monomers and Cl_l8-alkyl mercaptan, whereby the mercap~an actin~ as chain transferrer is incorporated as a terminal thioalkyl group.
The sulphur content introduced by the terminal thioalkyl groups must thereby be at least 90% by weight of the total sulphur present in the polymer. The content of sulphur possibly still present in the polymer, introduced, for Le A 23 559 ~, , ~s~
1 example, by incorporation of ini~iator fragments or by graft reaction of sulphur-containing emulsifiers,is less than 10% by weight of the total sulphur content in the polymer.
Examples of Cl_l8-alkyl mercaptans which can be used are ethyl mercaptan, n-propyl mercaptan, n-butyl mercaptan, tert.-butyl mercaptan, n-pentyl mercaptan, n-hexyl mercaptan, n-octyl mercaptan, n-decyl mercaptan, n-dodecyl mercaptan, tert.-dodecyl mercaptan, n-hexadecyl mercaptan and n-octadecyl mercaptan.
Preferred alkyl mercaptans are tert.-dodecyl mercaptan and n~dodecyl mercaptan or mixtures thereof.
The su~phur-containing polymers according to the invention which have limitin~ viscosities of from 2 to 15 ml/g (measured in DMF at 25C), are suitable as an agent for improving the flowability of ABS polymers in thermoplastic processing.
They are thereby added to the ABS polymers in quantities of from 0.5 to 15~ by weight, preferably from 1 to 10% by weight and particularly preferably from 1.5 to 7.5% by weight. Owing , to their content of terminal thioalkyl groups, they are, on the one hand, very effective as oxygen catchers, whereby the thioether grouping is converted into sulphoxide or sulphone groupings, on the other hand, the alkyl group, particularly a longer-chain grouping such as the dodecyl radical, contributes to an increased effectiveness as flowability improver.
Le A 23 559 `
~2~s~
1 Examples The invention is described in more detail in the followinq Examples. The given parts are parts by weight and in each case relate to solid constituents or polymer-isable constituents.
3.06 parts of styrene, 1.19 parts of acrylonitrile and 0.75 parts of tert.-dodecyl mercaptan are emulsified in 68 parts of water under nitroqen, together with 0.08 parts of the sodium salt of the disproportionated abietic acid, whereupon 0.3 parts of potassium persulphate (dissolved in 24 parts of water) are added and the mixture is heated to 65C. A mixture of 58.14 parts of styrene, 22.61 parts of acrylonitrile and 14.25 parts of tert.-dodecyl mercaptan as well as a solution of 1.92 parts of the sodium salt of the disproportionated abietic acid in over 25 parts of water are metered in over the course of 4 h, whereby the reaction temperature of 65C is maintained. After a period of secondary reaction, the latex is coagulated in a cold magnesium 5ul--; phate/acetic acid solution. The polymer obtained after drying at 70C, under vacuL~ in a yield of 97%, has a sulphur content of 2.3% and a limiting viscosity of 6.7 ml/g (in dimethyl formamide at 25C).
Example 2 3.10 parts of ~-methyl styrene, 1.40 parts of acryloni-trile and 0.50 parts of tert.-dodecyl mercaptan are emulsified in 80 parts of water under nitroqen together with 0.08 parts of the sodium salt of a Cg 18-alkyl su]phonic acid mixture, treated with 0.3 parts of potassium persulphate (dissolved in 15 parts of water) and heated to 70C. A mixture of 59.00 parts of ~-methyl styrene, 26.50 parts of acrylonitrile -; Le A 23 559 ~ ".
. .
.. .
, ,, ,. ;:
3~
9 _ 1 and 9.5 parts of tert.-dodecyl mercaptan as well as a solution of 1.92 parts of the potassium salt of a Cg 18-alkyl sulphonic acid mixture in 25 parts of water are then metered in over the course of 4 h, whereby the reaction temperature of 70C is maintained. After a period of secondary reaction, the latex is coagulated in a cold calcium chloride solution. After drying under vacuum at 70C, a polymer is obtained in a yield of 95~, with a sulphur content of 1.5 and a limiting viscosity of 10.9 ml/g (in dimethyl formamide at 25C).
E~ample 3 A mixture of 2.25 parts of styrene, 2.25 parts of methyl methacrylate and 0.50 parts of tert.-dodecyl mercaptan is emulsified in 80 parts of water under nitrogen with 0.08 parts of the sodium salt of the disproportionated abietic acid, treated with 0.3 parts of potassium persulphate (dissolved in 15 parts of water) and heated to 65C. A
: 20 mixture of 42.75 parts of styrene, 42.75 parts of methyl methacrylate and 9.5 parts of tert.-dodecyl mercaptan as well as a solution of 1.92 parts of the sodium salt of ``~ the disproportionated abietic acid in 25 parts of water are metered in over the course of 4 h, whereby the reaction temperature is maintained at 65C. After a period of secondary reaction, the latex is coagulated in a cold magnesium sulphate/acetic acid solution and the polymer is dried under vacuum at 70C. The polymer (yield 97%) has a sulphur content of 1.5% and a limiting viscosity of 6.0 ml/g (in DMF at 25C).
Example 4 3.15 parts of methyl methacrylate, 1.35 parts of acrylonitrile and 0.50 parts of tert.-dodecyl mercaptan are Le A 23 559 ~s~
1(~
1 emulsified in 80 parts of water under nitrogen ~ogether with 0.08 parts of the sodium salt of the disproportionated abietic acid, treated with 0.3 parts of potassium persulphate (dissolved in 15 parts of water) and heated to 65C. A
mixture of 59.85 parts of methyl methacrylate, 25.65 parts of acrylonitrile and 9.5 parts of tert.-dodecyl mercaptan as well as a solution of 1.92 parts of the sodium salt of the disporportionated abietic acid are in ~5 parts of water are metered in over the course of 4h, whereby the reaction temperature of 65C is maintained. After period of secondary re~ction the latex is coagulated in a cold magnesium su],phate/
~`~ acetic acid solution and the polymer is dried under vacuum at 70C. The polymer obtained in a yield of 96% has a sulphur content of 1.5% and a limiting viscositv of 9.Sml/g (in DMF at 25C).
Example 5 An ABS polymer, consisting of 40 parts of weight of a graft polymer of 36 parts by weight of styrene and 14 parts by weight of acrylonitrile on 50 parts by weight of a polybutadiene with an average particle diameter (d50) "` of 0.3 ~m and 60 parts by weight of a styrene-acrylonitrilecopolymer consisting of 72 parts by weight of styrene and 28 parts by weight of acrylonitrile with a Mw value of about 80 000 (MW/Mn-1~2.0) was treated with 4.2 parts by weight of the polymer in Example 1 and processed at 240C
to a spiral of about 8 mm in width and about 2 mm in depth.
by injection moulding. The length of the spiral was 51 cm.
DSC measurements on the pulverulent ABS polymer using - a DSC 2-measuring device by the firm Perkin-Elmer resulted in an induction time during the isothermic measurement at 160C (rinsing gas oxygen 3.6 l/h) up to the maximum oxidation rate of 67.4 min.
With the dynamic measurement (rinsing gas oxygen 3.6 l/h, heating rate 20 K/min) the maximum of the exothermic ` Le A 23 559 '~ . .
3~i 1 reaction was T = 220C.
Example 6 (comparison) The ABS polyrner described in Example 5 was processed under the same conditions without addition of the polymer in Example 1. The length of the spiral was 47 cm.
DSC measurements under identical conditions resulted for the isothermic measurement at 160C in an induction time up to the maximum oxidation rate of 3.8 min. With the dynamic measurement, the maximum of the exothermic reaction was T = 190.5C.
,~ O
Le A 23 559 . .
.
Mixtur 2 a) from 25 to 75 parts by weight, preferably from 30 to 70 parts by weight of (~-methyl)styrene and/or p-methyl styrene or vinyl toluene, b) from 25 to 75 parts by weight, preferably from 30 to 70 parts by weight of methyl methacrylate and c) as many parts by weight of a Cl_l8-alkyl mercaptan or mixtures thereof as produce a sulphur content of from 1.15 to 3.95~ by weight in the polymer; or d) from 7.5 to 25 parts by weight, preferably from 8 to 15 parts by weight of tert.-dodecyl mercaptan and/or n-dodecyl mer-captan or mixtures thereof;
. ' ' ~' '~ "''".
: - , .
, ~5~
Mixture 3 a) from lO to 60 parts by weigh-t, preferably .Erom 20 to 50 parts by weight of (~-methyl)styrene and/or p-rne-thyl styrene or vinyl toluene, b) from 10 to 60 parts by weigh-t, preferably from 20 to 50 parts by weight of methyl methacrylate, c) from 10 to 30 parts by weight, preferably from~ to 27.5 parts by weight of (meth)acrylonitrile and d) as many parts by weight of a Cl 18-alkyl mercaptan or mixtures thereof as produce a sulphur content of from 1.15 to 3.95% by weight in the polymer; or e) from 7.5 to 25 parts by weight, preferably from 8 to 15 parts by weight of tert.-dodecyl mercaptan. and/or n-dodecyl mer-captan or mixtures thereof;
Mixture 4 a) from 50 to 80 parts by weight, preferably from 55 to 75 parts by weight of methyl methacrylate, b) from lO to 30 parts by weight, preferably from 15 to 27.5 parts by weight of (meth)acrylonitrile and c) as many parts by weight of a Cl_lg-alkyl mercaptan or mixtures thereof as produce a sulphur content of from 1.15 to 3.95% by weight in the polymer; or d) from 7.5 to 25 parts by weight, preferably from 8 to 15 parts by weight of tert.-dodecyl mercaptan and/or n-dodecyl mer-captan or mixtures thereof.
' -Preferred sulphur-containing polymers are those which have a good compatibility with ABS polymers, particularly copolymers or terpolymer~ of (nuclear o~ side-chain substituted) styrene.
The production of the polymers according to the invention can take place in a known manner by solution-~
suspension-or emulsion polymerisation or by a combination of these processes, the polymerisation in emulsion is preferred.
This is preferably carried out using anionic emulsifiers such as sodium, potassium or ammonium salts of long-chain fatty acids having from 10 to 20 carbon atoms, for example potassium oleate, alkyl sulphates having from 10 to 20 carbon atoms, alkyl aryl sulphonates having from 10 to 20 carbon atoms or alkali or ammonium salts of diproportion-ated abietic acid.
The polymerisation reaction can be carried out in a wide temperature range, it preferably ta~es place between 30C
and 100C, particularly preferably between 50C and 80C.
Suitable radical-forming initiators are organic and inorganic peroxides, inorganic persulphates such as potassium persulphate, azoinitiators such as azobisisobutyronitrile, as well as redox systems which consist of an oxidizing agent, preferably a peroxide, and a reducing agent.. Potassium persulphate is used as preferred initiator, the quantities for use are between 0.1 and 0.5% by weight (based on the monomer quantity).
The introduction of the terminal thioalkyl groups takes place by polymerisation of a mixture of monomers and Cl_l8-alkyl mercaptan, whereby the mercap~an actin~ as chain transferrer is incorporated as a terminal thioalkyl group.
The sulphur content introduced by the terminal thioalkyl groups must thereby be at least 90% by weight of the total sulphur present in the polymer. The content of sulphur possibly still present in the polymer, introduced, for Le A 23 559 ~, , ~s~
1 example, by incorporation of ini~iator fragments or by graft reaction of sulphur-containing emulsifiers,is less than 10% by weight of the total sulphur content in the polymer.
Examples of Cl_l8-alkyl mercaptans which can be used are ethyl mercaptan, n-propyl mercaptan, n-butyl mercaptan, tert.-butyl mercaptan, n-pentyl mercaptan, n-hexyl mercaptan, n-octyl mercaptan, n-decyl mercaptan, n-dodecyl mercaptan, tert.-dodecyl mercaptan, n-hexadecyl mercaptan and n-octadecyl mercaptan.
Preferred alkyl mercaptans are tert.-dodecyl mercaptan and n~dodecyl mercaptan or mixtures thereof.
The su~phur-containing polymers according to the invention which have limitin~ viscosities of from 2 to 15 ml/g (measured in DMF at 25C), are suitable as an agent for improving the flowability of ABS polymers in thermoplastic processing.
They are thereby added to the ABS polymers in quantities of from 0.5 to 15~ by weight, preferably from 1 to 10% by weight and particularly preferably from 1.5 to 7.5% by weight. Owing , to their content of terminal thioalkyl groups, they are, on the one hand, very effective as oxygen catchers, whereby the thioether grouping is converted into sulphoxide or sulphone groupings, on the other hand, the alkyl group, particularly a longer-chain grouping such as the dodecyl radical, contributes to an increased effectiveness as flowability improver.
Le A 23 559 `
~2~s~
1 Examples The invention is described in more detail in the followinq Examples. The given parts are parts by weight and in each case relate to solid constituents or polymer-isable constituents.
3.06 parts of styrene, 1.19 parts of acrylonitrile and 0.75 parts of tert.-dodecyl mercaptan are emulsified in 68 parts of water under nitroqen, together with 0.08 parts of the sodium salt of the disproportionated abietic acid, whereupon 0.3 parts of potassium persulphate (dissolved in 24 parts of water) are added and the mixture is heated to 65C. A mixture of 58.14 parts of styrene, 22.61 parts of acrylonitrile and 14.25 parts of tert.-dodecyl mercaptan as well as a solution of 1.92 parts of the sodium salt of the disproportionated abietic acid in over 25 parts of water are metered in over the course of 4 h, whereby the reaction temperature of 65C is maintained. After a period of secondary reaction, the latex is coagulated in a cold magnesium 5ul--; phate/acetic acid solution. The polymer obtained after drying at 70C, under vacuL~ in a yield of 97%, has a sulphur content of 2.3% and a limiting viscosity of 6.7 ml/g (in dimethyl formamide at 25C).
Example 2 3.10 parts of ~-methyl styrene, 1.40 parts of acryloni-trile and 0.50 parts of tert.-dodecyl mercaptan are emulsified in 80 parts of water under nitroqen together with 0.08 parts of the sodium salt of a Cg 18-alkyl su]phonic acid mixture, treated with 0.3 parts of potassium persulphate (dissolved in 15 parts of water) and heated to 70C. A mixture of 59.00 parts of ~-methyl styrene, 26.50 parts of acrylonitrile -; Le A 23 559 ~ ".
. .
.. .
, ,, ,. ;:
3~
9 _ 1 and 9.5 parts of tert.-dodecyl mercaptan as well as a solution of 1.92 parts of the potassium salt of a Cg 18-alkyl sulphonic acid mixture in 25 parts of water are then metered in over the course of 4 h, whereby the reaction temperature of 70C is maintained. After a period of secondary reaction, the latex is coagulated in a cold calcium chloride solution. After drying under vacuum at 70C, a polymer is obtained in a yield of 95~, with a sulphur content of 1.5 and a limiting viscosity of 10.9 ml/g (in dimethyl formamide at 25C).
E~ample 3 A mixture of 2.25 parts of styrene, 2.25 parts of methyl methacrylate and 0.50 parts of tert.-dodecyl mercaptan is emulsified in 80 parts of water under nitrogen with 0.08 parts of the sodium salt of the disproportionated abietic acid, treated with 0.3 parts of potassium persulphate (dissolved in 15 parts of water) and heated to 65C. A
: 20 mixture of 42.75 parts of styrene, 42.75 parts of methyl methacrylate and 9.5 parts of tert.-dodecyl mercaptan as well as a solution of 1.92 parts of the sodium salt of ``~ the disproportionated abietic acid in 25 parts of water are metered in over the course of 4 h, whereby the reaction temperature is maintained at 65C. After a period of secondary reaction, the latex is coagulated in a cold magnesium sulphate/acetic acid solution and the polymer is dried under vacuum at 70C. The polymer (yield 97%) has a sulphur content of 1.5% and a limiting viscosity of 6.0 ml/g (in DMF at 25C).
Example 4 3.15 parts of methyl methacrylate, 1.35 parts of acrylonitrile and 0.50 parts of tert.-dodecyl mercaptan are Le A 23 559 ~s~
1(~
1 emulsified in 80 parts of water under nitrogen ~ogether with 0.08 parts of the sodium salt of the disproportionated abietic acid, treated with 0.3 parts of potassium persulphate (dissolved in 15 parts of water) and heated to 65C. A
mixture of 59.85 parts of methyl methacrylate, 25.65 parts of acrylonitrile and 9.5 parts of tert.-dodecyl mercaptan as well as a solution of 1.92 parts of the sodium salt of the disporportionated abietic acid are in ~5 parts of water are metered in over the course of 4h, whereby the reaction temperature of 65C is maintained. After period of secondary re~ction the latex is coagulated in a cold magnesium su],phate/
~`~ acetic acid solution and the polymer is dried under vacuum at 70C. The polymer obtained in a yield of 96% has a sulphur content of 1.5% and a limiting viscositv of 9.Sml/g (in DMF at 25C).
Example 5 An ABS polymer, consisting of 40 parts of weight of a graft polymer of 36 parts by weight of styrene and 14 parts by weight of acrylonitrile on 50 parts by weight of a polybutadiene with an average particle diameter (d50) "` of 0.3 ~m and 60 parts by weight of a styrene-acrylonitrilecopolymer consisting of 72 parts by weight of styrene and 28 parts by weight of acrylonitrile with a Mw value of about 80 000 (MW/Mn-1~2.0) was treated with 4.2 parts by weight of the polymer in Example 1 and processed at 240C
to a spiral of about 8 mm in width and about 2 mm in depth.
by injection moulding. The length of the spiral was 51 cm.
DSC measurements on the pulverulent ABS polymer using - a DSC 2-measuring device by the firm Perkin-Elmer resulted in an induction time during the isothermic measurement at 160C (rinsing gas oxygen 3.6 l/h) up to the maximum oxidation rate of 67.4 min.
With the dynamic measurement (rinsing gas oxygen 3.6 l/h, heating rate 20 K/min) the maximum of the exothermic ` Le A 23 559 '~ . .
3~i 1 reaction was T = 220C.
Example 6 (comparison) The ABS polyrner described in Example 5 was processed under the same conditions without addition of the polymer in Example 1. The length of the spiral was 47 cm.
DSC measurements under identical conditions resulted for the isothermic measurement at 160C in an induction time up to the maximum oxidation rate of 3.8 min. With the dynamic measurement, the maximum of the exothermic reaction was T = 190.5C.
,~ O
Le A 23 559 . .
.
Claims (24)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A sulphur-containing polymer of styrene, .alpha.-methyl styrene, p-methyl styrene, vinyl toluene, acrylonitrile or methyl methacrylate or a mixture thereof with a limiting viscosity of from 2 to 15 ml/g (measured in dimethyl formamide at 25°C) and a sulphur content of from 1.15 to 3.95% by weight, whereby at least 90% by weight of the incorporated sulphur is present as a con-stituent of terminal C1-18-thioalkyl groups.
2. Sulphur-containing polymer according to claim 1, when prepared by polymerizing a mixture of a) from 50 to 80 parts by weight, of (.alpha.-methyl)styrene or p-methyl styrene or vinyl toluene, b) from 10 to 30 parts by weight, of (meth)acrylonitrile and c) as many parts by weight of a C1-18-alkyl mercaptan or mixtures thereof as produce a sulphur content of from 1.15 to 3.95% by weight in the polymer.
3. A polymer according to claim 2 when prepared by polymerizing a mixture of 55 to 75 parts by weight of a) with 15 to 27.5 parts by weight of b).
4. Sulphur-containing polymer according to claim 2, when prepared by polymerizing a mixture of a) from 50 to 80 parts by weight, of (.alpha.-methyl)styrene or p-methyl styrene or vinyl toluene, b) from 10 to 30 parts by weight, of (meth)acrylonitrile and c) from 7.5 to 25 parts by weight, of tert.-dodecyl mercaptan or n-dodecyl mercaptan or mixtures thereof.
5. A polymer according to claim 4 when prepared by polymer-izing a mixture of 55 to 75 parts by weight of a) with 15 to 27.5 parts by weight of b) and 8 to 15 parts by weight of c).
6. Sulphur-containing polymer according to claim 1, when prepared by polymerizing a mixture of a) from 25 to 75 parts by weight, of (.alpha.-methyl)styrene or p-methyl styrene or vinyl toluene, b) from 25 to 75 parts by weight, of methyl methacrylate and c) as many parts by weight of a C1-18-alkyl mercaptan or mixtures thereof as produce a sulphur content of from 1.15 to 3.95% by weight in the polymer.
7. A polymer according to claim 6 when prepared by polymer-izing a mixture of 30 to 70 parts by weight of a) with 30 to 70 parts by weight of b).
8. Sulphur-containing polymer according to claim 6, when prepared by polymerizing a mixture of a) from 25 to 75 parts by weight, of (.alpha.-methyl)styrene or p-methyl styrene or vinyl toluene, b) from 25 to 75 parts by weight, of methyl methacrylate and c) from 7.5 to 25 parts by weight, of tert.-dodecyl mercaptan or n-dodecyl mercaptan or mixtures thereof.
9. A polymer according to claim 8 when prepared by polymer-izing a mixture of 30 to 70 parts by weight of a) with 30 to 70 parts by weight of b) and 8 to 15 parts by weight of c).
10. Sulphur-containing polymer according to claim 1, when prepared by polymerizing a mixture of a) from 10 to 60 parts by weight, of (.alpha.-methyl)styrene or p-methyl styrene or vinyl toluene, b) from 10 to 60 parts by weight, of methyl methacrylate, c) from 10 to 30 parts by weight, of (meth)acrylonitrile and d) as many parts by weight of a C1-18-alkyl mercaptan or mixtures thereof as produce a sulphur content from 1.15 to 3.95%
by weight in the polymer.
by weight in the polymer.
11. A polymer according to claim 10 when prepared by polymer-izing a mixture of 20 to 60 parts by weight of a) with 20 to 50 parts by weight of b) and 15 to 27.5 parts by weight of c).
12. Sulphur-containing polymer according to claim 10, when prepared by polymerizing a mixture of a) from 10 to 60 parts by weight, of (.alpha.-methyl)styrene or p-methyl styrene or vinyl toluene, b) from 10 to 60 parts by weight, of methyl methacrylate, c) from 10 to 30 parts by weight, of (meth)acrylonitrile and d) from 7.5 to 25 parts by weight, of tert.-dodecyl mercaptan or n-dodecyl mercaptan or mixtures thereof.
13. A polymer according to claim 12 when prepared by polymer-izing 20 to 50 parts by weight of a) with 20 to 50 parts by weight of b) and 15 to 27.5 parts by weight of c) and 8 to 15 parts by weight of d).
14. Sulphur-containing polymer according to claim l, when prepared by polymerizing a mixture of a) from 50 to 80 parts by weight, of methyl methacrylate, b) from 10 to 30 parts by weight, of (meth)acrylonitrile and c) as many parts by weight of a C1-18-alkyl mercaptan or mixtures thereof as produce a sulphur content of from 1.15 to 3.95% by weight in the polymer.
15. A polymer according to claim 14 when prepared by polymerizing 55 to 75 parts of a) with 15 to 27.5 parts of b).
16. Sulphur-containing polymer according to claim 14, when prepared by polymerizing a mixture of a) from 50 to 80 parts by weight, of methyl methacrylate, b) from 10 to 30 parts by weight, of (meth)acrylonitrile and c) from 7.5 to 25 parts by weight, of tert.-dodecyl mercaptan or n-dodecyl mercaptan or mixtures thereof.
17. A polymer according to claim 15 when prepared by polymerizing 55 to 75 parts of a) with 15 to 27.5 parts of b) and 8 to 15 parts of c).
18. A process for improving flowability of an ABS polymer or for protecting an acrylonitrile butadiene styrene (ABS) polymer against thermooxidative damage with a sulphur-containing polymer according to claim 1, 2 or 4 which process comprises admixing said ABS polymer with said sulphur containing polymer.
19. A flowable, thermooxidative-resistant ABS-based polymer comprising a mixture of an acrylonitrile butadiene styrene (ABS) polymer with a sulphur-containing polymer according to claim 1,2 or 4.
20. A process for preparing a sulphur-containing polymer of styrene, .alpha.-methyl styrene, p-methyl styrene, vinyl toluene, acrylonitrile or methyl methacrylate or a mixture thereof with a limiting viscosity of from 2 to 15 ml/g (measured in dimethyl formamide at 25°C), which process comprises polymerizing a monomer or monomer mixture of styrene, .alpha.-methyl styrene, p-methyl styrene, vinyl toluene, acrylonitrile or methyl methacrylate in the presence of a C1-18-alkyl mercaptan or a mixture thereof in quantities of from 4(0.503X + 1.222) % by weight to (1.728.X + 4.197) % by weight (based on the sum of the monomer and mercaptan quantity), whereby X represents the number of carbon atoms in the alkyl mercaptan.
21. A thermoplastic mixture containing a graft polymer A) a copolymer B) and a polymer C), which mixture comprises a sulphur-containing polymer C) of styrene, .alpha.-methyl styrene, p-methyl styrene, vinyl toluene acrylonitrile or methyl methacrylate or a mixture thereof with a sulphur content, introduced via terminal C1-18-thioalkyl groups, of from 1.15 to 3.95% by weight and a limiting viscosity of from 2 to 15 ml/g (measured in dimethyl formamide at 25°C) in quantities of from 0.5 to 15 parts by weight, based in each case on 100 parts by weight of a mixture of graft polymer A), copolymer B) and polymer C).
22. A thermoplastic mixture according to claim 21, wherein polymer C) is prepared by polymerizing a mixture of a) from 50 to 80 parts by weight, of (.alpha.-methyl)styrene or p-methyl styrene or vinyl toluene, b) from 10 to 30 parts by weight, of (meth)acrylonitrile and c) from 7.5 to 25 parts by weight, of tert.-dodecyl mercaptan or n-dodecyl mercaptan or mixtures thereof.
23. A thermoplastic mixture according to claim 22 wherein component a) comprises 55 to 75 parts by weight, component b) comprises 15 to 27.5 parts by weight and component c) comprises 8 to 15 parts by weight.
24. A thermoplastic mixture according to claim 21 or 22, which comprises A) from 5 to 80 parts by weight of a graft polymer consisting of A)1) from 5 to 90 parts by weight of a mixture of A)1)1) from 50 to 90% by weight of styrene, .alpha.-methyl-styrene, halogeno styrene, methyl methacrylate or a mixture thereof and A)1)2) from 50 to 10% by weight of (meth)acrylonitrile, methyl methacrylate, N-substituted maleimide or a mixture thereof, on A)2) from 95 to 10 parts by weight of a rubber with a glass temperature ? 10°C, and B) from 5 to 95 parts by weight of a thermoplastic copolymer with a Mw of from 15 000 to 200 000 (measured by light scatter or sedimentation) consisting of B)1) from 50 to 95% by weight of styrene, .alpha.-methyl styrene, halogeno styrene, methyl methacrylate or a mixture thereof, and B)2) from 50 to 5% by weight of (meth)acrylonitrile, methyl methacrylate, maleic acid anhydride, N-substituted maleimide or a mixture thereof, whereby the sum of the parts by weight of graft polymer A), copolymer B) and polymer C) is in each case again 100.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19853505747 DE3505747A1 (en) | 1985-02-20 | 1985-02-20 | SULFURIZED POLYMERISATE |
| DEP3505747.5 | 1985-02-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1255436A true CA1255436A (en) | 1989-06-06 |
Family
ID=6262959
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000502113A Expired CA1255436A (en) | 1985-02-20 | 1986-02-18 | Sulphur-containing polymers |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4740573A (en) |
| EP (3) | EP0196423A1 (en) |
| JP (2) | JPH085936B2 (en) |
| CA (1) | CA1255436A (en) |
| DE (3) | DE3505747A1 (en) |
| ES (1) | ES8707744A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3505747A1 (en) * | 1985-02-20 | 1986-08-21 | Bayer Ag, 5090 Leverkusen | SULFURIZED POLYMERISATE |
| DE3542468A1 (en) * | 1985-11-30 | 1987-06-04 | Bayer Ag | NEW STABILIZER SYSTEMS FOR POLYMERS I |
| JPH0714978B2 (en) * | 1987-09-24 | 1995-02-22 | 出光石油化学株式会社 | Styrene polymer and method for producing the same |
| US5206319A (en) * | 1991-08-19 | 1993-04-27 | Mitsui Toatsu Chemicals, Inc. | Process for preparing a toner resin, toner resin prepared thereby and toner composition containing particles of the toner resin |
| JP4320170B2 (en) * | 2002-12-27 | 2009-08-26 | 電気化学工業株式会社 | Styrenic resin and sheet thereof |
| DE102005060827A1 (en) | 2005-12-20 | 2007-06-28 | Lanxess Deutschland Gmbh | Graft rubbers with improved resistance to thermo-oxidative degradation |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1365506A (en) * | 1971-05-17 | 1974-09-04 | Ici Ltd | Preparation of acrylonitrile copolymers |
| US3960824A (en) * | 1971-07-09 | 1976-06-01 | Celanese Coatings & Specialties Company | Mercaptan initiated polymerization process carried out in the presence of oxygen |
| JPS5622323B2 (en) * | 1973-05-01 | 1981-05-25 | ||
| US4082818A (en) * | 1976-05-17 | 1978-04-04 | The Standard Oil Company | Mercaptan activation by acid in the copolymerization of acrylonitrile |
| JPS595201B2 (en) * | 1976-07-19 | 1984-02-03 | エヌオーケー株式会社 | Emulsion polymerization method using oligomers |
| US4246382A (en) * | 1977-11-11 | 1981-01-20 | Asahi Kasei Kogyo Kabushiki Kaisha | Solvent resistent acrylic resin and process for producing the same |
| JPS5516015A (en) * | 1978-07-19 | 1980-02-04 | Asahi Chem Ind Co Ltd | Styrene-acrylic resin and its production |
| JPS5556112A (en) * | 1978-10-23 | 1980-04-24 | Asahi Chem Ind Co Ltd | Novel copolymer and its preparation |
| DE3303864A1 (en) * | 1983-02-05 | 1984-08-09 | Bayer Ag, 5090 Leverkusen | THERMOPLASTIC MOLDS |
| US4510287A (en) * | 1983-11-21 | 1985-04-09 | Monsanto Company | ABS Compositions and process for preparing same |
| US4587313A (en) * | 1984-11-20 | 1986-05-06 | Hitachi Chemical Company, Ltd. | Radiation curable pressure-sensitive adhesive composition |
| DE3505747A1 (en) * | 1985-02-20 | 1986-08-21 | Bayer Ag, 5090 Leverkusen | SULFURIZED POLYMERISATE |
-
1985
- 1985-02-20 DE DE19853505747 patent/DE3505747A1/en not_active Withdrawn
-
1986
- 1986-02-07 EP EP86101590A patent/EP0196423A1/en not_active Withdrawn
- 1986-02-10 US US06/827,401 patent/US4740573A/en not_active Expired - Lifetime
- 1986-02-14 EP EP88105364A patent/EP0307537B1/en not_active Expired - Lifetime
- 1986-02-14 DE DE8686101889T patent/DE3671453D1/en not_active Expired - Lifetime
- 1986-02-14 DE DE8888105364T patent/DE3685441D1/en not_active Expired - Lifetime
- 1986-02-14 EP EP86101889A patent/EP0195918B1/en not_active Expired - Lifetime
- 1986-02-18 JP JP61032098A patent/JPH085936B2/en not_active Expired - Fee Related
- 1986-02-18 CA CA000502113A patent/CA1255436A/en not_active Expired
- 1986-02-19 ES ES552184A patent/ES8707744A1/en not_active Expired
-
1994
- 1994-10-19 JP JP6278548A patent/JP2701245B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| US4740573A (en) | 1988-04-26 |
| JP2701245B2 (en) | 1998-01-21 |
| EP0307537B1 (en) | 1992-05-20 |
| DE3685441D1 (en) | 1992-06-25 |
| JPS61192706A (en) | 1986-08-27 |
| ES552184A0 (en) | 1987-08-16 |
| JPH07179716A (en) | 1995-07-18 |
| EP0195918B1 (en) | 1990-05-23 |
| DE3505747A1 (en) | 1986-08-21 |
| JPH085936B2 (en) | 1996-01-24 |
| ES8707744A1 (en) | 1987-08-16 |
| EP0307537A2 (en) | 1989-03-22 |
| DE3671453D1 (en) | 1990-06-28 |
| EP0195918A2 (en) | 1986-10-01 |
| EP0307537A3 (en) | 1990-04-25 |
| EP0196423A1 (en) | 1986-10-08 |
| EP0195918A3 (en) | 1986-10-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1255436A (en) | Sulphur-containing polymers | |
| CA1091392A (en) | Mercaptan activation by acid in the copolymerization of acrylonitrile | |
| US3947527A (en) | Polymerizates of olefinic nitriles and diene rubbers | |
| CA1108344A (en) | Acrylonitrile-styrene-indene interpolymers | |
| US4338425A (en) | Process for preparing diene-containing rubbers having improved green strength | |
| US3891722A (en) | Process for manufacture of impact-resistant polymerizates of olefinic nitriles and diene rubbers | |
| CA1278629C (en) | Sulphur-containing graft products | |
| CA1111172A (en) | Rubber-modified acrylonitrile-vinyl ether-indene polymers | |
| US3629370A (en) | Process for the production of thermoplastic-elastic moulding compositions of high impact and notched impact strength | |
| CA1334696C (en) | Polyvinyl chloride resin composition | |
| CA1109180A (en) | Polymerizates of olefinic nitriles and diene rubbers | |
| JPS5813650A (en) | Thermoplastic resin composition | |
| US3100198A (en) | Blend of an alpha-methylstyrene/acrylonitrile copolymer with a copolymer of alpha-methylstyrene and a diolefin having styrene and acrylonitrile grafted thereon | |
| KR0131573B1 (en) | Process of copolymer having high heat resistance | |
| JPS5861108A (en) | Thermoplastic resin and its preparation | |
| CA1077187A (en) | Impact-resistant acrylonitrile copolymer process | |
| US3839495A (en) | Impact-resistant olefinic-nitrile copolymers | |
| JPH0689218B2 (en) | Molding composition having uniform particle size and improved thermal stability | |
| KR960000569B1 (en) | Process for producing a nitrile resin having a good impact resistance | |
| KR0131574B1 (en) | Composition of copolymer having heat resistance and preparation method using them | |
| CA1111174A (en) | Rubber-modified acrylonitrile-styrene-indene interpolymers | |
| KR800001071B1 (en) | Composition of olefin nitrol and dien rubber polymer resin | |
| US4163766A (en) | Impact-resistant olefinic-nitrile olefinic-ester copolymers prepared in the presence of an olefinic-ester copolymer elastomer | |
| KR810000396B1 (en) | Mercaptan activation by acid in the copolymerization of acrylonitrile | |
| JPS63280712A (en) | Rubber-reinforced high nitrile resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |